Assessing the organic composition of urban surface films using nuclear magnetic resonance spectroscopy.

Recently it has been shown that urban surfaces are covered with a thin film which mediates the fate, distribution and accumulation of semi-volatile organic compounds in the environment. In this study we apply a combination of solution, semi-solids, and solid state nuclear magnetic resonance (NMR) methods to provide a general overview of the organic constituents. In surface film collected from 30 m2 of outside windows over an area of 12 km2 in downtown Toronto, we roughly estimate that the organic carbon is approximately 35% carbohydrate, approximately 35% aliphatics, approximately 20% aromatics, and approximately 10% carbonyl groups. Various aliphatic groups can be identified including a number of acids, alcohols, alkanes, and alkenes. Also, numerous intact aliphatic esters are apparent that have not been observed before, as well as carbohydrates. The aromatic species include a small portion that appears to be derived from a polymer of styrene, in addition a larger fraction is consistent with polyhydroxylated PAH derived material, although this assignment is tentative and based solely on 1-D NMR data only. In addition, signals from polybutadiene are present and while accurate quantification is not possible, it appears that this polymer may be up to a few percents by weight of the total organic material.

Analysis and elimination of artifacts in indirect covariance NMR spectra via unsymmetrical processing.

Indirect covariance NMR offers an alternative method of extracting spin-spin connectivity information via the conversion of an indirect-detection heteronuclear shift-correlation data matrix to a homonuclear data matrix. Using an IDR (inverted direct response)-HSQC-TOCSY spectrum as a starting point for the indirect covariance processing, a spectrum that can be described as a carbon-carbon COSY experiment is obtained. These data are analogous to the autocorrelated 13C-13C double quantum INADEQUATE experiment except that the indirect covariance NMR spectrum establishes carbon-carbon connectivities only between contiguous protonated carbons. Cyclopentafuranone and the complex polynuclear heteroaromatic naphtho[2',1':5,6]-naphtho[2',1':4,5]thieno[2,3-c]quinoline are used as model compounds. The former is a straightforward example because of its well-resolved proton spectrum, while the latter, which has considerable resonance overlap in its congested proton spectrum, gives rise to two types of artifact responses that must be considered when using the indirect covariance NMR method.